Triazine derivatives possessing aphicidal properties



' ane sulphonates and isothionates.

UnitedStates Patent Oflice 3,169,904 Patented Feb. 16, 1965 This application is a continuation-in-part of Serial No. 764,498 and Serial No. 21,134, both now abandoned. The entire subject matter of each of these prior applications is incorporated herein by reference.

This application is a division of our copending application, Serial No. 290,196, filed June 24, 1963.

The invention relates to new organic compounds and more particularly it relates to triazine derivatives which possess valuable aphicid'al properties.

According to the invention therefore we provide s-triazine derivatives of the formula:

wherein R and R stand for methyl or ethyl radicals, wherein R R R and R which may be the same or different, stand for hydrogen or for lower alkyl radicals or, R and R or, R and may be joined, together with the adjacent nitrogen atom, to form a piperidine ring, and

wherein X stands for an oxygen or a sulphur atom, and the salts thereof. i

As suitable salts of thesaid s-triazine derivatives there may be mentioned salts derived from inorganic acids for example hydrochlorides and'salts derived from organic acids for example oxalates, p-toluene sulphonates, meth- As suitable examples of lower alkyl radicals (R R R and R there may be mentioned methyl, ethyl, propyl and butyl radicals.

Preferred compounds of the present invention are 2-diethoxyphosphinothioylthiomethyl 4:6 diamino-s-triazine, 2 diethoxyphosphinylthiomethyl-4;6-diamino striazine, 2 'dimethoxyphosphinothioylthiomethyl 4:6-

7 diamino s-triazine, 2-dimethoxyphosphinylthiomethyl- 4:6 diamino-s-triazine, Z-dimethoxy-phosphinothioyl- *thiomethyl-4-arnino=6-methylamino-s-triazine and 2-dimethoxyphosphinothioylthiomethyl 4-amino-6dimethy1 amino-s-triazine.

According to a further feature 'of the invention we provide a process for the manufacture "of the 's-triazine deri- 'vatives which comprises interaction of a compound of the formula: a Q

wherein R R and X have the meaning stated above and wherein M stands for an alkali metal, for example so dium, or an ammonium radical, and a compound of the formula:

wherein R R R and R have the meanings stated above and wherein Y stands for a halogen atom;

As a suitable halogen atom there may be mentioned for example chlorine, bromine or iodine. The reaction may be carried out Within the temperature range of 20- 150 C. and preferably by heating the reactants together in an inert'solvent or diluent for example a lower alcohol for example methanol or ethanol.

The halomethyl-s-triazines used as starting materials maybe obtained either by interaction ofa compound of the formula;

YCI-I -C0OR V wherein Y has the meaning stated above and' R stands for a lower alkyl radical, and a corresponding biguanide of the formula: I

i NRaR4 N RsRa wherein R R R and R have the meaning. stated above, provide that R R R and R do not all stand for alkyl radicals, or by reaction of the corresponding diazomethyl-s-t'riazine derivative with gaseous hydrogen halide for and a biguanidebf the formula? example gaseous hydrogenchloride.

According to a'further feature of the inventionwe provide a process for the manufacture of some of the s-triazine derivatives which comprises interaction of a compound of the formula: v I

' Ri0\ X R295 senicooai wherein R ,,R R and X have'the meaning stated above,

NRaR4 Nn=c B 1 Nit-=01 NRsRt wherein R R R andRg have the meaning stated above,

provided that at least one of R ,R R and R stands for hydrogen.

. The reaction may be carried out in the presence of an inert diluent-or solvent for;example methanoh The O:O'-dialkyl swalkoxycarbonylmethylphosphorotlfiolates andthiolothionates used as starting materials in the above process may be obtained by interaction of a compound of the formula:

RiO X wherein R R X and M have the meaning stated above.

and a compound of the formula:

Y-CHg-COOR7 wherein R and Y have the meaning stated above.

The s-triazine derivatives with which this invention is concerned possess outstanding selective aphicidal activity. They display very high contact, residual and systemic properties against aphid species and they are also of value as aphicidal seed dressings. They are also highly toxic to I certain other injurious insets and mites. They possess low phytotoxic properties.

Thus according to yet a further feature of the invention we provide insecticidal compositions containing at least one of the s-triazine derivatives described above,

in admixture with suitable diluents or carriers.

As suitable compositions there may be mentioned for example. aqueous formulations wherein the active ingredient, in the form of the base or a salt thereof, is I dissolved or dispersed in aqueous media for example,

water which may contain organic solventsfor example methanol, .tetrahydrofurfuryl. alcohol or B-ethoxyethanol and also suitable wetting or dispersing agents or other suitable auxiliary agents known to the art to be used in the preparationof such aqueous formulations. A suit able wetting or dispersing agent is the condensation product of ethylene oxide with an alkyl phenol for example the product obtained from the condensation product of octyl-cresol with-about-7e8 molecular proportions of ethylene oxide. Preferred compositions are those containing between 0.000l% and 0.1% by weight of active ingredient.

The insecticidal compositions may also be in the form of seed dressingswherein the active ingredient is admixed with an inert pulverulent solid for example fullers earth, talc, kaolin or bentonite. The said dressings may be applied to seeds-for example delinted cotton seed at a rate of between 1% and 8% by weight of the seed and the young planteventually obtained from the dressed seed are protected, against "aphid infestations for example.

against Aphis gossypii.

As stated above, the s-triazine derivativespossess; selective aphicidal properties and-the insecticidal compositions described above show activity against aphid infestations such fas -Macrosiphum pisi and Aphis fabae.

I The-invention is illustrated but not limited by the following examples in which'the partsare by weight:

Example I A mixture of 42 parts of 2-chloromethyl-4:G-diamino- .55

s-triazine, 57 parts of sodium O-:O'-diethyl-1 hosphorothioate and 320 parts of ethanol is stirred and heated 7 under refluxfor six hours. It is then allowed to cool and stand for 20 hours and is then filtered. The solid residue thus'obtained is boiled with ethanol and the mixture is filtered. The filtrate, is cooled and there is obtained 2-diethoxy-phosphinylthiomethyla4:6 diamino-striazine as a crystalline product. M.P. 169 C.

The hydrochloride is prepared ,by dissolving the above compound in. alcoholic hydrochloric acid and allowing the solution to stand for afevv minutes. It has M.P. 144+ 146 C. with decomposition and it is readily soluble in water,

' Example 2 8 parts :of 2-chloromethyl-4:6-diamino-s-triazine. are

added to a solution of 10:45 parts of sodium .OzOi-diethylphosphorodithioate in '80 parts of ethanol. and :tliev 'mixture is stirred and heated under refluxfor seven hours.

The mixture. is cooled and filtered and the 1 solid residue 4 is washed with water. It is crystallised from ethanol and there is thus obtained '2-diethoxyphosphinothioylthiomethyl-4:o-diamino-s-triazine, M.P. 168169 C.

The hydrochloride may be prepared by passing hydrogen chloride into a solution of the base in ethyl acetate. It has M.P. l74-175 C.

The hydrogen oxalate may be prepared by mixing a A solution of 14 parts of O:O'-'diethyl S-ethoxycarbonylmethyl 'phosphorothiolothi-onate in parts of.

methanol is stirred, and a warm solution of 5 parts of biguanide in 300 parts of methanol is added gradually during a period of two hours. Stirring is continued for a further three hours and the mixture is then allowed to stand for a further sixteen hours. The mixture is filtered and the solid residue so obtained is Z-diethoxyphosphin-v othioylthior'nethyll:G-diarnino-s-triazine. M.P. 169 C., identical with the product ofExample 2.

The O:O'-diethyl S-ethoxycarbonylmethyl phosphoro-.

thiolothionate usedas starting material may be obtained as follows: I

93 parts of O:O'-diethyl phosphorodithioic acid are added with cooling to a solution of sodium ethoxide (prepared from 11.5 parts of sodium) in 240 parts of ethanol.

0.25 part of sodium iodide is added-and,6l.3 parts of ethyl chloracetate are then run in with stirring during 40 minutes. The mixture is heated under reflux for .two hours and is then treated with 5 parts of water. The mixture is filtered and the filtrate is evaporated under reduced pressure to remove; most of the ethanol. The residue is treated with water and ether and the ether extract isseparated, washed'twice With water and dried over sodium sulphate. The ether is removed and distillation yields: O:10'-diethyl S-ethoxycarbonylmethylphosphorothiolothionate, B.P. 105-107 C./0.00'5 mm. n

Example 4 V. A' mixture of 8' parts of 2-chloromethyl-4z6 bis- (methylamino)-s-triazine, 7.5 parts of sodium O:O-diethyl phosphorothiol ate, 160 parts of ethanol and 40 parts of benzene is stirred and heated vunder reflux for 6 The reaction mixture is allowed to cool and is then' filtered. The filtrate is evaporated to dryness under. reduced pressure and the residue is taken up in '67 parts, of chloroform. The mixture -is;filtered and the filtrate is hours.

evaporated. The residual solid is crystallised from ethyl acetate and there is thus obtained 2-diethoxyphosphinyl-; thiomethyl 4:6-bis-(methylaminoys-triazine, M.P. 134- 136 C.

usedas starting materialmay be prepared as follows:

' The 2-chloromethyl-4:6-bis-,(methylan1ino)-s triazine 33.1 parts of -1:5-dimethylbiguanide .dihydrochloride are added to a solution of sodium methoxide. prepared from 7.6 parts of sodium and 160 parts of methanol; The

mixture is heated under reflux for four hoursand is then filtered. -20 partsof ethyl chloroa cetate are then added to the filtrate at ordinary temperature during thirty .min- A -utes and the solution is allowed to stand for 16 hours. The mixture is filtered and the. solid residue is crystallised fromv p-ethoxyethanol to give 2-chlorometh'yl-4z6 bis- (methylarnino)-s-triazine, M.P. 228 C. a

Examplefi 1A solution of 15.8, parts of O:O-dimethyl phosphoro- 'dithioic acid in parts of methanol is treated with 5.3

parts of anhydrous sodium carbonate. 15.9 parts of 2- chloromethyl-4:6-diamino-s-triazine are then added and the mixture is heated under reflux for 7 hours. The reaction mixture is then cooled and filtered and the solid residue is Washed with water and dried. It is crystallised from aqueous methanol or aqueous ,B-ethoxyethanol and there is thus obtained 2-dimethoxyphosphinothioylthiomethyl-4:6-diamino-s-triazine. M.P. 164l66 C.

2.8 parts of the above base are dissolved in a solution of 1 part of methanesulphonic acid in 10 parts of water by stirring at 50-60 C. The solution is cooled and filtered and the solid residue so obtained is Z-dimethoxyphosphinothioylthiomethyl 4:6 diamino s triazine methanesulphonate, M.P. 160-162" C.

Example 6 A mixture of 9.2 parts of sodium O:O'-dimethyl phosphorothiolate, 8.0 parts of 2-chloromethyl-4:6-diamino-striazine and 65 parts of methanol is heated under reflux for 18 hours and the reaction mixture is then cooled and filtered. The solid residue is freed from sodium chloride by washing with Water. It is then crystallised from water and there is thus obtained Z-dimethoxyphosphinylthiomethyl-4:G-diamino-s-triazine, M.P. 198 C.

Example 7 6.9 parts of sodium are reacted with 120 parts of methanol and 19 parts of l-methylbiguanide hydrochloride are then added. The mixture is heated under reflux for 3 hours and cooled, and then 24.5 parts of ethyl The residue is treated with water and the aqueous mixture is filtered. The solid residue is crystallised from Water and there is thus obtained Z-diethoxyphosphinylthiomethyl-4-amino-6-methylamino-satriazine M.P. 81- 83 C.

Example 8 7.9 parts of O:O'-dimethyl phosphorodithioic acid in 64 parts of methanol are neutralised at a temperature of 20-30" C. by passing in dry ammonia gas with cooling. 8.7 parts of 2-chloromethyl-4-amino 6 methylamino-striazine are then added and the mixture is heated under reflux for 90 minutes. The reaction mixture is concentrated under reduced pressure and then filtered and the filtrate is diluted with water and cooled. The aqueous mixture is filtered and the solid residue is crystallised from aqueous methanol and there is thus obtained 2-dimethoxyphosphinothioylthiomethyl-4-amino 6 methylamino-s-triazine, M.P. 126127 C.

Using an equivalent quantity of 2-chloromethyl-4- amino-6-dimethyl-amino-striazine in place of the 2-chloromethyl-4-amino-6-methylamino-s-triazine used as starting material, there is obtained in a similar manner, an oil which solidifies on cooling. It is crystallised from aqueous methanol and there is thus obtained 2-dimethoxyphosphinothioylthiomethyl-4-amino 6 dimethylamino-s-triazine, M.P. 77-79 C. The 2-chloromethyl-4-amino-6-dimethylamino-s-triazine used as starting material may be obtained by the process as described in Example 9.

Example 9 23 parts of sodium are dissolved in 400 parts of ethanol and 55 parts of 1:1-dirnethylbiguanide hydrochloride are added. The mixture is heated under reflux for 2 hours and cooled, and is then treated during minutes with 82 parts of ethyl chloroacetate. After two hours the 9 reaction mixture is filtered and the solid residue is crystallised from aqueous ethanol thus providing 2 chloromethyl-4-amino 6 dimethylamino-s-triazine, M.P. 181-- Example 10 A mixture of 2.4 parts of O:O'-diethyl S-ethoxycarbonylmethyl phosphorothiolate, 1.3 parts of 1:5-dimethylbiguanide and parts of dry pyridine is stirred at a temperature of 18-23 C. for 6 hours and is then allowed to stand for about 18 hours. The reaction mixture is filtered and the filtrate is evaporated under reduced pressure. The residue is dissolved in ethanol and again evaporated to complete the removal of pyridine. The crystalline residue is recrystallised from isobutanol and there is thus obtained 2-diethoxyphosphinylthiomethyl- 4:6 -bis(methylamino)-s-triazine, M.P. 134-136 C., identical with the product described in Example 4.

O:O'-diethyl S-ethoxycarbonylmethyl phosphorothiolate may be prepared by the following procedure:

69 parts of diethyl phosphite are added to 320 parts of alcohol in which 11.5 parts of sodium have been dissolved. 16 parts of sulphur are then added in small portions, so that the temperature does not exceed 50 C. 61.4 parts of ethyl chloroacetate are next added and the reaction mixture is heated under the reflux for 2 hours and then cooled. The bulk of the alcohol is removed by evaporation and the residue is treated with ether and water. The ethereal extract is separated, Washed with Water, dried over anhydrous sodium sulphate and then distilled. There is thus obtained O:O-diethyl-S-ethoxycarbonylrnethyl phosphorothiolate, B.P. 96 C./0.01 mm.

. is crystallised from aqueous ethanol.

'ture of l8-23 C. for 6 hours.

Example 11 I A mixture of 9.5 parts of IiS-dimethyl-biguanide, 20.4

' parts of O:O-diethyl S-ethoxycarbonyl-methyl phosphorotniolothionate and parts of ethanol is stirred at a temperature of 1823 C. during-24 hours. The mixture is then filtered and the solid residue is Washed with ethanol. There is thus obtained 2 diethoxyphosphinothioylthiomethyl 4:6 bis (methylaminoQ-s-triazine, M.P. 131- The hydrochlorideof this base is prepared by dissolving 3 parts of the above compound in 20 parts of con- I centrated aqueous hydrochloric acid and then filtering the reaction mixture after one hour. There. is thus obtained 2 diethoxyphosphinoth-ioylthiomethyl 4:6 bis- (methylamino)-s-triazine hydrochloride, M.P. 134- 137 C.

Example 12 thiomethyl-4-amino-6 -ethyl-amino-s-triazine hydrochloride, M.P. 149-151 c.

oxide. plants which are then infested with Macrosiplzam pisi, a

Example 13 110 parts of ethanol and the mixture is then heated under The reaction mixture is filtered and reflux for 7 hours. the filtrate is evaporated under reduced pressure. The residual oil is dissolved in ether and the ethereal solution 'is washed with water, 'driedover anhydrous sodium sulphate and then'evaporated. The residual oil is dissolved in ethanol and the solution is treated with alcoholic picric acid. The. mixture is filtered and the solid residue is crystallised'from ethanol. There is thus obtained 2-diethoxyhosphinylthiomethyl-4-amino 6 piperidino-s-triazine .picrate, M.P.166-168" C. When this picrate is stirred in aqueous ethanol with the hydroxide form of 'Ainberlite resinIRA-400, there is obtained Z-diethox'yphosphinylthiomethyl-4-amino 6 piperidino-s-triazine, M.P. 112114 C. Example 14 A solution of 2.3 parts of 1-n-butylbiguanide and 4.0 parts of O:O-diethyl S-ethoxycarbonylmethyl phosphorothiolothionate in 25 parts of ethanol is allowed to stand at a temperature of 18-23 C. for 24 hours. The solvent is then removed by evaporation under reduced pressure and the residue is dissolved in ether. The ethereal solution is Washed with water, dried over anhydrous sodium sulphate and evaporated. The residual oil is treated with alcoholic picric acid and there is thus obtained the picrate It is then crystallised from aqueous of 2 diethoxy-phosphinothioylthiomethyl-4-amino-6-nbutylamino-s-triazine, M.P. 127-130 C.

' Example 1 5 The process described in Example 1 is repeated except i that the 2-chloromethyl-4:6-cliamino-s-triazine usedas starting material is replaced by an equivalent quantity of 2-bromomethyl-4:6-diamino-s-triazine. There is thus obtained in a similar manner 2-diethoxyphosphinylthiomethyl-4:G-diamino-s-triazine, M.P. 169 C., identical with the product obtained in Example 1.

The process described above is repeated except that the 2-bromomethyl-4:6-diamino-s-triazine used as starting material is replaced by .an equivalent quantity of 2-iodomethyl-4:o-diamino-s-triazine. in a similar manner, Z-diethoxyphosphinylthiomethyl-4:6- diamino-s-triazine, M.P. 169 (3., identical with the prodnot obtained in Example 1.

The 2-bromomethyl-4:6-diamino-s-triazine used as starting material is prepared by adding ethyl bromoacetate (167 parts) slowly to biguanide .(101 parts) in methanol (800 parts) at 0 C. The mixture is filtered and the solid residueis crystallised from aqueous alcohol to give the desired product, M.P. 226-229 C.

80 parts of 2-diethoxyphosphinothioylthio-methyl-4:6- diamino-s-triazine are dissolved in 10,000 parts of methanol and the solution is poured into 1,000,000 parts of water containing 500 parts of the condensation product of I octylcresol with 7-8 molecular proportions of ethylene When this preparation is sprayed on to broadbean 100% hill of the latter is obtained withinj24 hours.

There'is. again obtained,

In a similar man-- net, the use of ethyl iodoacetate (214 parts) in place of two days.

sprayed with it.

8 Example 17 8 parts'of Z-diethoxyphosphinylthiomethyl-4: 6-diaminos-triazine hydrochloride are dissolved in. 1,000,000 parts of water containing'500 parts of the condensation product of octylcresol with 7.8 molecular proportions of ethylene oxide. When Macrosiphum pisi are sprayed with this preparation, 97% of the aphids are killed within 24 hours.

Example 18 8 parts of 2-diethoxyphosphinylthiomethyl4:6-diamino: s-triazineare dissolved in 1000parts of methanol and the solutionis diluted with 100,000 parts of water containing 50 parts of the condensation product of octylcresol with7-8 molecular proportions of ethylene oxide. When broad bean plants are sprayed With this preparation and then infested three days later with Aphis fabae, a kill of the-aphids results indicating that the preparation has marked residual aphicidal activity.

Example 19 1 part of 2-diethoxyphosphinylthiomethyl 4:6-diaminos-triazine is dissolved in 20 parts of methanol and the solution is poured into 2000 parts of water containing 1 part of the condensation product of octylcresol with 7-8 molecular proportions of ethylene oxide. When a pair of leaves half-Way up the stem of a broad bean plant intested with A phis fabae is immersed in this preparation a'complete kill of aphids above the immersed leaves is obtained in less than 24 hours, and below the leaves in There'are no phytotoxic. symptoms, and the preparation therefore possesses valuable systemic activity.

. Example 20 A seed dressing is prepared by ball-milling equal parts of 2-diethoxyphosphinylthiomethyl-4:6-diainino-s-triazine and'fullers earth for 8 hours. Delinted cotton seed is dressed at the rate of 8% by weight with this preparation before planting. The seedlings eventually obtained are completely protected against continuous infestation by A plzis gossypii for at least three weeks;

. Example 21 I 100 parts of 2-diethoxyphosphinylthiomethyl 4:6-diamino-s-triazine hydrochloride are dissolved in 1,000,000

parts of Water containing 500 parts of the condensation product of octylcresol with 7-8 molecular proportions of ethylene oxide.

. ExampleZZ 1 part of 2-dimethoxyphosphinothioylthio-methyl-4:6-

diamino-s-triazine is dissolved in 5 parts of tetrahydrofurfuryl alcohol at 50 C. and the solution is added to, il00,000-parts of water containing 50 parts of the condensation product of ootylcresol with 7-8 molecular proportions of ethylene oxide; This preparation gives a 100% hill of Macrosiphum pisi on plants which are Example 23 1 part of-Z-dimcthoxyphosphinothioylthiornethyl-4 6-diamino-s-triazine is added to 5 parts of water containing 0.56 part of isothionic acid (Z-hydroxyethanesulphonic acid) with stirring. The resulting solution is mixed with 10,000 parts of water containing 5 parts of'the condensation product of octylcresol with 7-8 molecular proportions of ethylene oxide. Plants sprayed with this solution are protected against infestation by aphid species According to the present invention we also provide new s-triazine derivatives of the formula:

in which'R and R are methyl or ethyl radicals; R is a hydrogen atom; R R and R which can be the same or different, are such a hydrogen atom or a methyl, ethyl, propyl or butyl radical, or R and R together with their adjacent nitrogen atom constitute a piperidino ring; R, is a methyl, ethyl, propylor butyl radical; and X is an oxygen or a sulphur atom; and acid addition salts thereof. 7

Compounds which in particular have been found to possess useful aphicidal activity are those in which the groups R R and R togetherhave a total number of carbon atoms not exceeding six, and especially where R;

is a hydrogen atom.

In general, the aphicidal activity of the compounds of the invention decreases with increase in the number of carbon atoms in group R, which is preferably a methyl radical. I V

The acid addition salts of the present invention can be salts derived from an inorganic acid, for example hydrochlorides, or from an organic acid, for example oxalates, p-toluene sulphonates, methane sulphonates or isothionates. 1

The invention also includes aprocess for the preparation of s-triazine derivatives, in which a compound of the formula:

is reacted with a haloalkyl-s-triazine of the formula:

RsRe where R R R R R R R and X have any of the meanings given to them above; M is an atom of an alkali metal, for example sodium, or an ammonium radical; and Y is a halogen atom, for example bromine. The process is preferably performed within the temperature range -150 C. though the temperature chosen naturally depends to a large extent upon the reactivity of the reactants. Preferably the reactants are in solution or dispersion in a suitable solvent or diluent,'for examplewater or a lower alcohol such as methanol or ethanol.

The haloalkyl s-triazine used as starting material in the process described above can be obtained by a process 7 inwhich a compound of the formula:

. containing, as active ingredient, a compound of the in vention or an acid addition salt thereof, in admixture with a suitable diluent or carrier. The'pesticidal compositions can, for example, be a liquid composition in which the active ingredient is dissolved or dispersed in a suitable liquid medium, or it can be a powder composition.

The compounds of the invention have only low solubilityin water, but are in general sufiiciently soluble to enable aqueous solutio'nsof low pesticidal concentration tobe prepared. However, in order to facilitate the preparation of aqueous solutions, especially where higher pesticidal concentrations are required, .it has been found advantageous to dissolve the compound initially in a small quantity ofmethanol, tetrahydrofurfuryl alcohol, diacetone alcohol or B-ethoxyethanol, and to dilute the resulting organic solution with suflicient water to obtain the desired aqueous solution.

Where the pesticidalcompositions of the invention is a powder composition, the active ingredient can be in,

admixture with an inert powder diluent, for example fullers earth, talc, kaolin, kieselguhr or bentonite. If desired, the pesticidal compositions, whether liquid or solid, can contain a suitable wetting ordispersing agent or other suitable auxiliary agent known in the art as being useful in pesticidal compositions. The powder pesticidal compositions referred to above can be used as seed dressings for the trestment of seed in order to provide protection against aphid attack for plants, subsequently grown. from the seed.

.The invention also includes a method of combating aphids, for'example Macrosiphum pisi, in which the aphids, or plants susceptible to attack by aphids are treated with a compound or'a pesticidal composition of 7 this invention.

The invention is illustrated by the following examples in which (exceptwhere otherwise stated) the parts'referred to are parts by weight.

Example 24 collected by filtration and thoroughly washed with water,

and. the solution heated under reflux for 7 hours after which themixture was cooled and filteredgthe filtrate concentrated, and then diluted with several volumes of water. On 1 standing,- 2-st-(diethoxyphosphinylthio)ethyl-4:6-diamino-s-triazine, MP. 167-9" 'C. was obtained as a crystalline product.

This product has been tested and found to be active against the aphid species Macr osiphum' pisi. The compound was tested in the formof a number of aqueous solutions covering a range of concentrations, and each containing 0.5 by weight of a Wetting agent. Similar aqueous solutions of various concentrations of the commercial pesticide parathion were used as a standard for comparison.

The method of testing against M. pisi was as follows:

Adult, apterous, viviparous females were sprayed under I a Potter Tower apparatus with 2 cc. of each of the aqueousjsolutionsof the test chemical and of parathion, three replicatesof 30 10 aphids being used with each solution.

After being sprayed, the aphids were transferred to 2-02. 7

ber of deadaphids was counted and-the'LD. 50iflv alue f calculated. 1

Using the LD 50 values and parathion, the parathion equivalent obtained was 2.5,

thus illustrating the eifectiveness of the test compound against Mr piszl. Example 25 This example illustrates the activity of, the product of Example 24 against a second aphid species, A'phis fabae. Z-u-('diethoxyphosphinylthio) ethyl-4:6;diamino-s tri azine (16 parts) was dissolved in methanol (1000 parts) and the solution diluted withwater (100,000parts) containing 50 parts of the condensation product of octylcresol with 78 molecularproportionsof ethylene oxide. When. broad bean plants were sprayedwiththis pesticidal compositionand then infested three days later. with Aphis fabae, a 100% killof the aphids was obtained indicating that the preparation has marked residual 'aphicidal activity. 7 f i Examplel26 The hydrochloride of 2-m-(diethoxyphosphinylthio) ethyl-4:6-diamino-s-triazine was prepared by dissolving the latter compound in ethyl acetate and passing hydrogen chloride into the solution. The hydrochloride was 1 obtained as asolid having a melting point of :155l56 C.

with decomposition.

. Example 27 i This example describes the preparation of Z-oc-(diethoxyphosphinothioylthio)-propyl-4-arnino -"6 methyl 'amino-s-triazine.

Sodium (2.3 parts) was dissolved in methanol (80' parts), methyl biguanide dihydrochloride (11 parts) was added, and the mixture agitated at room temperature for thirty minutes. The sodium chloride which had separated i out was removed by filtration and ethyl wbrornobutyrate parts) added to, the filtrate. After standing at room temperature for 24 hours tthe solution was evaporated to dryness leaving a gum, which on recrystallization from a obtained for the test chemical l2 2-a-(diethoxyphosphinylthio) ethyl-4: 6-diamin0-s tri azine hydrochloride (16 parts) was dissolved in water (1 mixture of benzene and petroleum ether afiorded. Z-abromo-propyl-4-amino-fi-rhethylamino-s-triazine, MP. 66- 70 C. The latter compound (2.8 parts) and ammonium -0,0-dime,thyl phosphorodithioate (2.0 parts) were dis Example 28 'This example describes the preparation "of Z-oz-(dicthoxyphosphinylthio) -n-amyl 4 -diarnino-s-triazine.

Biguanide (2.9 parts) and ethyl a-bromohexoate (6.4 parts) were dissolved in methanol (40 parts) and the solution allowedto stand at room temperature for 2v weeks. At theend of that time the solution was. evapethylene oxide.

million parts) containingSOll parts of the condensation product of octylcresol with 78 molecular proportions of Whatwe claim is:

1. An insecticidal composition comprising, as the essen-' tial active ingredient, at least one compound which in free base form has the formula:

wherein R and R are selected from the group consisting of methyl and, ethyl; R and R are selected from the group consisting of hydrogen and loweralkyl; R and R are selected from the group consisting of hydrogen, lower :alkyl and taken together, the atoms necessary to complete.

a piperidino ringwith their adjacent nitrogen atoms; R,

is selected from the. group consisting of hydrogen and lower .alkyl; andX is selected from the group consisting of oxygen. and sulphur atoms, together with a carrier therefor and a dispersing agent.

2. A process for the improvement of seed, which 'comprises treating the, seed, before sowing, with a compound which in free base form has the formula;

wherein R and R are selected from the group consisting or methyl and ethyl; R and R are selected from the 7 group: consisting of hydrogen and lower alkyl; Rgand R orated to dryness. and the residue thus obtained was recrystallized from aqueous methanol giving 2-u-bromoamyl-4:6-diamino-s-triazine, MJP. 158160 C. The latter compound '(2.0'p'arts). and sodiumTO-,O-dimethylphosphorothioate (1.3 parts) were dissolved in methanol (20 parts)" and the solution heated under reflux for 9 hours; The solution was then cooled, filtered to remove sodium bromide which had separated out and evaporated to dryness leaving 2-d-(dimethoxyphosphinothioyl)-namyl 4z6-diamino-s triazine. 7

, sample 29 r This example illustrates the eilectivenessiof the hydro chloride of Example 26 against the aphid species M. pisi;

are selected from the group consisting of hydrogen," lower alkyl and taken together, the atoms necessary to complete a'piperidino ring with their adjacent nitrogen atoms; R; is selected from the group consisting of .hydrogennand lower alkyl and X is selected from the group consisting.

of oxygen and sulphur atoms. r

3. A process for controlling aphid species which comprises applying to an area subject to attack by said aphid species,'an, efiective amount of at least one compound which in free base form has the formula:

wherein R and R are selected from the group'consisting of methyl and ethyl;'R and R are selected from the group consisting of hydrogen and lower alkyl; ;R and R are selected from the group consisting of;hydroge n, lower alkyl and taken together, the atoms necessary to complete awpiperidino ringwith their adjacent nitrogen atoms; R;

is selected from the group consisting of hydrogen and lower alkyl; and X is selected from the group consisting of oxygen and sulphur atoms. 2 g V 4. The process. of claim 3 wherein said. compound is '2 dimethoxyphosphinothioylthiornethyl 4:6 diarnino-sr triaziner 5. Theprocess of claimd-wherein said compound is 2 diethoxy-phosphinothioylthiornethyl 4:6 diarnino-striazine; f a r 6.. The process of 2-diethoxy-phosphinylthiomethylki 6-diamino-s-triazine;

When broad bean plants infected with Macrosiphum pisi were sprayed with this pesticidal com position, of the aphids were killed within 24 hours.

claim 3 wherein said compound is 7. The process of claim 3 wherein said compound is 2-dimethoxyphosphinylthiomethy1-4: 6-diam-ino-s-triazine.

8. The process of claim 3 wherein said compound is 2 methoxyphosphinothioylthiomethyl-4-amino-6-methylamino-s-tn'azine.

9. The process of claim 3 wherein said compound is 2-dimethoxyphosphinothioylmethyl 4 amino-6-methyl- 2 dirnethoxyphosphinothioylthiomethyl 4 amino-6-dimethylamino-s-triazine.

10. The process of claim 3 wherein said compound is 2-oc- (diethoxyphosphinylthio) ethyl-4: 6-diamino-s-triazine.

11. The process of claim 3 wherein said compound is Z-oc- (diethoxyphosphinylthio) ethyl 4: 6 diamino s triazine hydrochloride.

14 2-a-(dimethoxyphosphinylthio)-n-amyl 4:6 diamino-striazine.

13. The process of claim 3 wherein said compound is 2-a-(dimethoxyphosphinothioylthio)propyl 4 amino-6- methylamino-s-tniazine.

References Cited by the Examiner UNITED STATES PATENTS 2,822,364 2/58 Schuller 260-2499 2,848,451 8/58 Schuller 260-2499 2,887,432 5/59 Baker et a1. 16733 2,911,337 11/59 Uhlenbroek et a1. 167-33 12. The process of claim 3 wherein said compound is 15 JULIAN S- VI Prim ry m ner- 

1. AN INSECTICIDAL COMPOSITION COMPRISING, AS THE ESSENTIAL ACTIVE INGREDIENT, AT LEAST ONE COMPOUND WHICH IN FREE BASE FORM HAS THE FORMULA: 